AT O M I C A B S O R P T I O N
T E C H N I C A L
Sensitivity Versus Detection Limit
The earliest atomic absorption
(AA) spectrometers provided
results in terms of percent
absorption (%A = 100 – %T).
Those early instruments were
significantly less stable than
today's modern equipment,
and virtually all analyses were
performed with no scale expan-
sion. For most elements, the
smallest concentration which
could be detected was that which
produced a percent absorption
signal of about 1%A (0.0044
absorbance units) which became
accepted as a rough measurement
of performance known as
“sensitivity”, a term used with
emission spectroscopy and
other techniques. However,
improvements in AA systems
soon permitted the use of high
degrees of scale expansion,
allowing the determination of
concentrations much lower than
that represented by the sensitivity
value. The term “detection limit”
was coined to mean the lowest
concentration that could be
detected by atomic absorption.
The change in the terminology
used to describe the smallest
detectable quantity by AA had
an unfortunate side effect –
the frequent (and erroneous)
interchangeable use of the terms
“sensitivity” and “detection limit”.
w w w. p e r k i n e l m e r. c o m
N O T E
The difference between
sensitivity and detection
limit
Sensitivity is a measure only of
signal magnitude, the solution
concentration or weight of an
element that produces a signal
of 0.0044A (1%A) for continuous
or peak height measurements or
0.0044 A•s for integrated peak
area. It is also known as charac-
teristic concentration with flame
AA or characteristic mass with
furnace AA.
For a visual representation of the
Detection limit is a measure of difference between sensitivity
the smallest concentration which and detection limit, refer to the
can be determined with a speci- signals above. Signals A and B
fied precision or reproducibility. represent the same concentration
Most frequently, the specified and give comparable absorbances
precision is defined in terms or signal (S). The sensitivities are,
of the concentration producing therefore, the same. However, the
a signal equivalent to three times better signal stability or lower
the standard deviation of a series “noise” level (N) of signal B
of blank (baseline) readings or will provide better reproducibility
readings for a standard with (precision) and allow smaller
a concentration close to the concentrations to be accurately
anticipated detection limit. measured. Signal B will provide
This definition is equivalent to better precision and detection
a 99% confidence level. That is, limits because it has a better (i.e.,
the answer obtained under these higher) signal-to-noise ratio (S/N).
conditions will be correct 99
times out of 100.
As defined, the detection limit is
a function of both signal strength
(or sensitivity) and signal stability.
Greater sensitivity alone will not signal-to-noise ratios for the two Detection limits are direct indicators
provide better detection limits or signals are therefore the same of system performance, since both
precision as illustrated by signals (S/N = 8 for each). As a result, detection limits and performance
C and D, which again are for the performance should also be the are functions of the signal-to-noise
same concentration. The system same for the two systems. ratio.
which produced signal C provided
Sensitivity alone cannot be related to
twice the signal or sensitivity of that
system performance, since it is only
which produced signal D but also
an indication of signal strength.
generated twice the noise level. The

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